CN107841325B - Method for preparing synthesis gas by pyrolyzing biomass-blended high-ash papermaking sludge - Google Patents
Method for preparing synthesis gas by pyrolyzing biomass-blended high-ash papermaking sludge Download PDFInfo
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- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 19
- 239000007789 gas Substances 0.000 claims abstract description 62
- 238000000197 pyrolysis Methods 0.000 claims abstract description 46
- 239000000843 powder Substances 0.000 claims abstract description 45
- 239000002028 Biomass Substances 0.000 claims abstract description 38
- 238000001035 drying Methods 0.000 claims abstract description 8
- 239000012159 carrier gas Substances 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 5
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- 238000010438 heat treatment Methods 0.000 abstract description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 10
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 8
- 238000002309 gasification Methods 0.000 description 7
- 229910052783 alkali metal Inorganic materials 0.000 description 6
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- 229910052784 alkaline earth metal Inorganic materials 0.000 description 5
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- 239000001569 carbon dioxide Substances 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
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- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
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- 241000411851 herbal medicine Species 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
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- 150000002894 organic compounds Chemical class 0.000 description 1
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- 238000009270 solid waste treatment Methods 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
- C10B53/02—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of cellulose-containing material
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B57/00—Other carbonising or coking processes; Features of destructive distillation processes in general
- C10B57/08—Non-mechanical pretreatment of the charge, e.g. desulfurization
- C10B57/10—Drying
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B57/00—Other carbonising or coking processes; Features of destructive distillation processes in general
- C10B57/18—Modifying the properties of the distillation gases in the oven
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Treatment Of Sludge (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a method for preparing synthesis gas by pyrolyzing biomass-blended high-ash papermaking sludge. The method comprises the following steps: respectively drying, crushing and sieving the biomass and the sludge to obtain biomass fine powder and sludge fine powder, wherein the mass ratio of the biomass fine powder to the sludge fine powder is 1-3: 1, mixing biomass fine powder and sludge fine powder, and sealing and storing for later use; placing the mixed fine powder in a feeder, continuously introducing pyrolysis carrier gas, opening a tubular furnace to set a target temperature after air in the system is exhausted, transferring the mixed fine powder in the feeder into a reactor after the temperature in the furnace is raised to the target temperature, and heating the mixed fine powder in the reactor to carry out pyrolysis to generate non-condensable gas, tar and biological semicoke; and (4) after the pyrolysis gas is discharged from the reactor, sequentially passing through a condensing device and a gas purifying device, drying and storing. The method of the invention can not only improve the gas yield of the synthesis gas in the pyrolysis, but also reduce the yield of the biological tar in the pyrolysis.
Description
Technical Field
The invention relates to the field of industrial solid waste treatment and recycling, in particular to a method for preparing synthesis gas by pyrolyzing biomass blended high-ash papermaking sludge.
Background
China is the biggest Chinese herbal medicine producing and consuming country in the world at present, and more than 1500 medicine enterprises produce more than one thousand and five million tons of waste traditional Chinese medicine residues every year. The traditional treatment mode of the waste traditional Chinese medicine dregs mainly depends on direct landfill, so that on one hand, the environmental pollution is serious, and part of medicine residues still exist in the dregs, which easily causes the pollution of underground water and generates pungent gas, and on the other hand, the traditional treatment mode is also a waste of resources. How to cleanly and efficiently utilize the waste Chinese medicine residues becomes an important problem to be solved urgently.
Paper sludge is a major by-product of the paper industry and comprises water, fibers, organic compounds, inorganic salts and inorganic fillers. The ash content in the sludge is up to 50-70%, the main components comprise metal elements such as calcium, magnesium, sodium, aluminum and the like, the traditional treatment method mainly adopts direct landfill, the serious pollution is caused to the land, and the method is not environment-friendly and uneconomical.
Pyrolysis gasification is regarded as a promising technology for converting carbon-rich solid waste into clean fuel gas, and is receiving wide attention. Researches show that the calorific value of fuel gas generated by gasifying the Chinese medicine residues is 5000kJ/Nm3The above results show that the traditional Chinese medicine residues have good gasification application potential. However, the large amount of tar produced by the biomass in pyrolysis remains a great challenge for pyrolysis gasification applications, tar condenses in pipelines below the dew point, and excess tar easily corrodes and blocks fuel pipelines, filtering devices, and downstream equipment. How to solve the problem of high content of gas-producing tar in pyrolysis gasification becomes a hotspot of current gasification research. The traditional tar removal methods comprise a spraying method, a bubbling water bath method, a dry filtering method and a proper combination of the methods, which belong to physical purification and cannot really remove tar. The catalytic cracking method is the most effective and most advanced method at present, and the catalytic cracking method is to crack macromolecular tar into various small molecular gases (such as hydrogen, carbon monoxide, methane, carbon dioxide and the like) at high temperature or in the presence of a catalyst, and the small molecular gases are gradually adopted in large and medium-sized gasification furnaces. The existing commonly used tar catalysts comprise nickel-based catalysts, alkali metal catalysts, ore catalysts and the like, and a large number of researches show that the alkali metal and alkaline earth metal elements have obvious catalytic action on biomass tar. If the high-ash papermaking sludge rich in alkali metal and alkaline earth metal elements is added in the pyrolysis gasification of the traditional Chinese medicine residues, the alkali metal and alkaline earth metal elements in the sludge greatly catalyze the cracking conversion of tar at high temperature, so that macromolecular tar is cracked into small molecular gas, the yield of the tar is reduced, and the yield of the gas in the co-pyrolysis is improved.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a method for preparing synthesis gas by pyrolyzing biomass blended with high-ash papermaking sludge, which can improve the gas production rate of the synthesis gas in pyrolysis and reduce the yield of biological tar in pyrolysis.
In order to solve the problems of the prior art, the invention adopts the technical scheme that:
a method for preparing synthesis gas by pyrolyzing biomass blended high-ash papermaking sludge comprises the following steps:
step 1, drying, crushing and sieving the biomass and the sludge respectively to obtain biomass fine powder with the particle size of 0.2-0.45mm and sludge fine powder with the particle size of less than 0.125mm, wherein the mass ratio of the biomass fine powder to the sludge fine powder is 1-3: 1, mixing biomass fine powder and sludge fine powder, and sealing and storing for later use;
and 3, discharging the pyrolysis gas from the reactor, sequentially passing through a condensing device and a gas purifying device, drying and inputting the pyrolysis gas into a gas collecting bag.
The improvement is that the mass ratio of the biomass fine powder to the sludge fine powder in the step 1 is 3: 1.
the improvement is that the biomass in the step 1 is traditional Chinese medicine residues, and the sludge raw material is high-ash sludge generated in the paper-making process.
The improvement is that the pyrolysis carrier gas in step 2 is nitrogen.
As a modification, the target temperature set for the line in step 2 was 900 ℃.
The improvement is that the condensing medium of the condensing device in the step 3 is an ice-water mixture; the purifying medium of the gas purifying device consists of water, a glass fiber filter membrane and allochroic silica gel.
Has the advantages that:
1. the invention provides a method for preparing synthesis gas by using biomass and papermaking sludge together. The pyrolysis of biomass and papermaking sludge is carried out in a fixed bed reactor, and a large amount of ash rich in alkali metal and alkaline earth metal in the sludge is utilized to have a certain catalytic action on tar generated in the pyrolysis of the biomass, so that the yield of the tar in a pyrolysis product is reduced;
2. according to the method, on the premise of not increasing an additional device, the tar yield in the biomass pyrolysis process is reduced through the blending of the high-ash papermaking sludge, the macromolecular tar is converted into the micromolecular gas, and the synthesis gas yield of unit raw materials is improved;
3. the method effectively utilizes two industrial wastes of the traditional Chinese medicine residues and the papermaking sludge, realizes the reduction and utilization of the traditional Chinese medicine residues and the sludge, and reduces the pollution of the treatment of the traditional Chinese medicine residues and the sludge to the environment.
Drawings
FIG. 1 is a system setup for synthesis gas production in an example of the invention, wherein 1-pyrolysis carrier gas tank, 2-feeder, 3-tube furnace, 4-reactor, 5-condensing unit, 6-gas purification unit, 7-gas drying unit, and 8-gas collection unit.
Detailed Description
The present invention will be described in further detail below with reference to specific examples.
The invention takes the traditional Chinese medicine residue of a Chinese patent medicine factory in Henan and the paper making sludge of a paper making factory in Shandong as raw materials, and carries out industrial analysis and element analysis on the traditional Chinese medicine residue and the paper making sludge, and the results are respectively shown in tables 1 and 2.
TABLE 1 Industrial analysis and elemental analysis of herb residue
TABLE 2 Industrial and elemental analysis of papermaking sludge
Example 1
The system is assembled as shown in fig. 1.
A method for preparing synthesis gas by pyrolyzing biomass blended high-ash papermaking sludge comprises the following steps:
step 1, drying, crushing and sieving the biomass and the sludge respectively to obtain biomass fine powder with the particle size of 0.2-0.45mm and sludge fine powder with the particle size of less than 0.125mm, wherein the mass ratio of the biomass fine powder to the sludge fine powder is 3: 1, mixing biomass fine powder and sludge fine powder to obtain mixed fine powder, and sealing and storing for later use;
and 3, discharging the pyrolysis gas from the reactor, sequentially passing through a condensing device and a gas purifying device, and then entering a gas collecting bag.
Wherein the condensing device controls the condensing temperature through an ice-water mixture, and tar in the pyrolysis gas is absorbed by isopropanol in the condensing device when passing through the condensing device;
the gas purification device can remove a small amount of uncondensed tar and moisture remained in the pyrolysis gas.
The composition and content of the gas in the gas collection bag were measured and the results are shown in table 3.
Table 3 table of gas components prepared in example 1
The control group was: under the same condition, biomass fine powder and sludge fine powder with the same mass are respectively pyrolyzed to obtain the weighted average value of the gas content.
The results show that the yield of hydrogen is improved by 18.4 percent compared with that of single pyrolysis, the yield of carbon monoxide is improved by 35.2 percent compared with that of single pyrolysis, and the yield of methane is improved by 18.9 percent compared with that of single pyrolysisPercent, the yield of the carbon dioxide is improved by 71.3 percent compared with that of the carbon dioxide which is pyrolyzed separately, and the total gas yield is 0.309Nm3The yield of tar is 8.8g/kg, and is reduced by 16.0% compared with single pyrolysis.
Example 2
The same procedure as in example 1 was repeated, except that the temperature of the line in step 2 was set to 700 ℃.
The syngas components produced in example 2 were tested and the data is shown in table 4.
Table 4 table of gas components prepared in example 2
The control group was: under the same condition, biomass fine powder and sludge fine powder with the same mass are respectively pyrolyzed to obtain the weighted average value of the gas content.
The results show that the yield of hydrogen is increased by 29.6 percent compared with that of single pyrolysis, the yield of carbon monoxide is reduced by 3.0 percent compared with that of single pyrolysis, the yield of methane is reduced by 14.2 percent compared with that of single pyrolysis, the yield of carbon dioxide is increased by 15.5 percent compared with that of single pyrolysis, and the total yield of gas is 0.128Nm3The yield of tar is 31.4g/kg, and is reduced by 20.9% compared with single pyrolysis.
Example 3
The mass ratio of the biomass-removing fine powder to the sludge fine powder is 1: 1, the rest of the same procedure as in example 1.
The syngas components produced in example 3 were tested and the data is shown in table 5.
Table 5 table of gas components prepared in example 3
The control group was: under the same condition, biomass fine powder and sludge fine powder with the same mass are respectively pyrolyzed to obtain the weighted average value of the gas content.
The results show that the yield of hydrogen is improved by 29.0 percent compared with the single pyrolysis, the yield of carbon monoxide is improved by 64.7 percent compared with the single pyrolysis,the yield of methane is reduced by 24.5 percent compared with that of single pyrolysis, the yield of carbon dioxide is improved by 64.3 percent compared with that of single pyrolysis, and the total yield of gas is 0.295Nm3The yield of tar is 4.6g/kg, and is reduced by 34.2% compared with single pyrolysis.
From the above results, it can be seen that a method of co-producing synthesis gas from biomass and paper sludge. The pyrolysis of biomass and papermaking sludge is carried out in the fixed bed reactor, and a large amount of ash rich in alkali metal and alkaline earth metal in the sludge is utilized, so that the tar generated in the pyrolysis of the biomass has a certain catalytic action, and the yield of the tar in a pyrolysis product is reduced.
In addition, the present invention is not limited to the above embodiments, and may be implemented in various ways without departing from the scope of the invention.
Claims (6)
1. A method for preparing synthesis gas by pyrolyzing biomass blended high-ash papermaking sludge is characterized by comprising the following steps: step 1, drying, crushing and sieving the biomass and the sludge respectively to obtain biomass fine powder with the particle size of 0.2-0.45mm and sludge fine powder with the particle size of less than 0.125mm, wherein the mass ratio of the biomass fine powder to the sludge fine powder is 1-3: 1, mixing biomass fine powder and sludge fine powder, and sealing and storing for later use; step 2, placing the mixed fine powder in a feeder, continuously introducing pyrolysis carrier gas at the speed of 150ml/min, after exhausting air in the system, opening a tubular furnace to set a target temperature of 500-; and 3, discharging the pyrolysis gas from the reactor, sequentially passing through a condensing device and a gas purifying device, drying and inputting the pyrolysis gas into a gas collecting bag.
2. The method for preparing the synthesis gas by pyrolyzing the biomass-blended high-ash papermaking sludge according to claim 1, wherein the mass ratio of biomass fine powder to sludge fine powder in the step 1 is 1-3: 1.
3. the method for preparing the synthesis gas by pyrolyzing the biomass blended with the high-ash papermaking sludge according to claim 1, wherein the biomass in the step 1 is traditional Chinese medicine residues, and the sludge raw material is the high-ash sludge generated in the papermaking process.
4. The method for preparing the synthesis gas by pyrolyzing the biomass-blended high-ash papermaking sludge according to claim 1, wherein the pyrolysis carrier gas in the step 2 is nitrogen.
5. The method for preparing the synthesis gas by pyrolyzing the biomass-blended high-ash papermaking sludge according to claim 1, wherein the target temperature set by the tubular furnace in the step 2 is 900 ℃.
6. The method for preparing the synthesis gas by pyrolyzing the biomass-blended high-ash papermaking sludge according to claim 1, wherein the condensing medium of the condensing device in the step 3 is an ice-water mixture; the purifying medium of the gas purifying device consists of water, a glass fiber filter membrane and allochroic silica gel.
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| CN109135785A (en) * | 2018-10-10 | 2019-01-04 | 辽宁科技大学 | A kind of method of sludge and biomass copyrolysis processing activated sludge |
| CN110724547A (en) * | 2019-04-10 | 2020-01-24 | 湖南顶立科技有限公司 | Method for drying and pyrolyzing sludge and medicine residues cooperatively |
| CN111777309A (en) * | 2020-06-28 | 2020-10-16 | 华中师范大学 | Sludge treatment method capable of reducing discharge |
| CN111995210A (en) * | 2020-07-29 | 2020-11-27 | 华中师范大学 | Method for preparing combustible gas by co-pyrolysis of sludge and biomass |
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| CN107163991A (en) * | 2017-05-25 | 2017-09-15 | 天津大学 | Utilize the method for biomass by hydrolyzation residue and the common vaporizing system of sludge for biosynthesis gas |
| CN107117787A (en) * | 2017-07-07 | 2017-09-01 | 中国石油大学(华东) | A kind of process of oily sludge addition microalgae biomass collaboration pyrolysis |
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